The synthesis, spectroscopic characterization, computational analysis, and photoelectrochemical behavior of a new iron-based chromophore, [(Cpy)2Fe (deeb)](PF6)2 (Fe(Cpy)2(deeb)), where Cpy is1-methyl-3-(2-pyridyl)imidazole and deeb is 4,4’-(CO2CH2CH3)2-2,2’-bipyridine, is reported. Electrochemically reversible wavesassignedtoametal-centeredEo(FeIII/II)=+0.48andaligand-centeredEo(Fe2+/+) =−1.47VvsFc+/0 reduction were evident in cyclic voltammetry measurements. The combination of a strong σ-donor and a π-acceptor lowered the energy of the metal-to ligandcharge-transfer(MLCT)excitedstaterelativetothemetal-centeredstate. Two MLCT transitions appear in the visible region at 424 and 580nm. TDDFT calculations revealed that the lower-energy band was well formulated as Fe(II)→deeb, and the higher-energy transition was charge transfer to both the deeb and Cpy ligands. Resonance Raman spectroscopy supports these findings showing enhanced deeb vibrational modes with532nm excitation, both deeb and Cpy modes with 473nm excitation, and exclusively Cpy with 405nm excitation. Ultrafast spectroscopy reveals a short-lived (∼2ps) MLCT excited state and a longer-lived (∼20ps) metal-centered state. Efficient methods to deprotect the ester groups and anchor the complex to mesoporous TiO2 (anatase) thin films in high surface coverages, Fe (Cpy)2(dcb)|TiO2σ=3×10−8mol/cm2, were established. Pulsed light excitation of Fe(Cpy)2(dcb)|TiO2 resulted in rapid excited state injection (kinj>108s−1) and formation of a charge-separated state, FeIII(Cpy)2(dcb)|TiO2(e), which persists on the millisecond time scale before returning cleanly to the ground state with second order kinetics. Injection yields measured 50 ns after light excitation were found to double from Φ=0.15 with green (532nm) light to 0.30 with blue (457nm) light excitation. Incident photon-to-current efficiency (%IPCE)measurements as a function of excitation wavelength in a 0.5MLiI/I2/CH3CN electrolyte provide clear evidence for band-selective “hotcarrier” injection from the remote Cpy-localized excited state. Collectively, the spectroscopic and photoelectrochemical data indicate that a semiconductor can intercept hot electrons from iron chromophores even when the excited-state dipole is oriented away from the surface-anchoring ligand.